US6440891B1 - Catalyst comprising a complex of a metal of subgroup VIII, on the basis of a phosphonite ligand and method for hydroformylation - Google Patents

Catalyst comprising a complex of a metal of subgroup VIII, on the basis of a phosphonite ligand and method for hydroformylation Download PDF

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US6440891B1
US6440891B1 US09/623,175 US62317500A US6440891B1 US 6440891 B1 US6440891 B1 US 6440891B1 US 62317500 A US62317500 A US 62317500A US 6440891 B1 US6440891 B1 US 6440891B1
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alkyl
group
catalyst
hydroformylation
alkoxy
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Heiko Maas
Rocco Paciello
Michael Röper
Jakob Fischer
Wolfgang Siegel
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/65719—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonous acid derivative
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • the present invention relates to a catalyst comprising a complex of a VIIIth transition group metal other than nickel with at least one bi- or more highly dentate phosphonite ligand wherein the phosphorus and one of the oxygen atoms of the phosphonite group are part of a from 5- to 8-membered heterocycle, and to a process for hydroformylating compounds containing at least one ethylenically unsaturated double bond in the presence of such a catalyst.
  • the hydroformylating or oxo process is widely used for the large scale production of aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes may optionally be hydrogenated with hydrogen in the same operation to form the corresponding oxo alcohols.
  • the reaction itself is highly exothermic and generally takes place under elevated pressure and temperature in the presence of catalysts.
  • the catalysts used are cobalt, rhodium or ruthenium compounds or complexes which may be promoted with amine or phosphine ligands. Additional promoters have hitherto not achieved any significance in the industry.
  • the hydroformylation reaction gives rise to the formation of isomeric aldehyde mixtures because of the possible CO addition to each of the two carbon atoms of a double bond.
  • the double bond may isomerize from an internal into a terminal position.
  • the n-aldehyde is generally favored over the iso-aldehyde, but because of the significantly greater industrial importance of the n-aldehydes it is desirable to optimize the hydroformylation catalysts with regard to achieving a greater n-selectivity.
  • WO 95/30680 describes bidentate phosphine ligands where the two phosphine groups are both bonded to an aryl radical and these two aryl radicals form a doubly bridged, ortho-fused ring system in which one of the two bridges consists of an oxygen or a sulfur atom.
  • Rhodium complexes based on these ligands are useful as hydroformylation catalysts, and the hydroformylation of terminal olefins provides a good n/iso ratio.
  • the disadvantage of these chelated phosphines is their difficulty of preparation, so that industrial processes which rely on such chelated phosphine catalysts are at an economic disadvantage.
  • U.S. Pat. No. 4,169,861 describes a process for preparing terminal aldehydes by hydroformylating ⁇ -olefins in the presence of a rhodium hydroformylation catalyst based on a bidentate ligand and a monodentate ligand.
  • the preferred bidentate ligand is 1,1′-bis(diphenylphosphino)ferrocene.
  • the monodentate ligand is preferably a phosphine, such as diphenylethylphosphine.
  • U.S. Pat. No. 5,312,996 describes a process for preparing 1,6-hexanedial by hydroformylating butadiene in the presence of hydrogen and carbon monoxide.
  • the hydroformylation catalysts used are rhodium complexes with polyphosphite ligands wherein the phosphorus and two of the oxygen atoms of the phosphite group are part of a 7-membered heterocycle.
  • JP-A 97/255 610 describes a process for preparing aldehydes by hydroformylation in the presence of rhodium catalysts comprising a monodentate phosphonite ligand.
  • hydroformylation catalysts based on bi- or more highly dentate phosphonite ligands wherein the phosphonite group is part of a 5- to 8-membered heterocycle.
  • catalysts based on complexes of a metal of the VIIIth transition group which comprise at least one bi- or more highly dentate phosphonite ligand wherein the phosphonite group is part of a from 5- to 8-membered heterocycle.
  • the present invention accordingly provides a catalyst comprising a complex of a VIIIth transition group metal other than nickel with a bi- or more highly dentate phosphonite ligand of the general formula I
  • n 0 or 1
  • A combines with that part of the phosphonite group to which it is attached to form a 5- to 8-membered heterocycle which may optionally be additionally singly, doubly or triply fused with cycloalkyl, aryl and/or hetaryl, in which case the fused-on groups may each bear one, two or three substituents selected from the group consisting of alkyl, alkoxy, halogen, nitro, cyano and carboxyl,
  • R 1 is a C 3 - to C 6 -alkylene bridge which may have one, two or three double bonds and/or may be singly, doubly or triply fused with aryl and/or hetaryl, in which case the aryl or hetaryl groups may bear one, two or three substituents selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cycloalkyloxy, aryloxy, halogen, trifluoromethyl, nitro, cyano, carboxyl and NE 1 E 2 , where E 1 and E 2 are identical or different and each is alkyl, cycloalkyl or aryl,
  • alkyl denotes both straight-chain and branched alkyls.
  • Alkyl is preferably straight-chain or branched C 1 -C 8 -alkyl, more preferably C 1 -C 6 -alkyl, particularly preferably C 1 -C 4 -alkyl.
  • alkyl groups are especially methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl
  • Cycloalkyl is preferably C 5 -C 7 -cycloalkyl, such as cyclopentyl, cyclohexyl or cycloheptyl.
  • Substituted cycloalkyl preferably has 1, 2, 3, 4 or 5, especially 1, 2 or 3, substituents selected from the group consisting of alkyl, alkoxy and halogen.
  • Aryl is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl or naphthacenyl and especially phenyl or naphthyl.
  • Substituted aryl preferably has 1, 2, 3, 4 or 5, especially 1, 2 or 3, substituents selected from the group consisting of alkyl, alkoxy and halogen.
  • Hetaryl is preferably pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
  • Substituted hetaryl preferably has 1, 2 or 3 substituents selected from the group consisting of alkyl, alkoxy and halogen.
  • alkyl, cycloalkyl and aryl apply mutatis mutandis to alkoxy, cycloalkyloxy and aryloxy.
  • NE 1 E 2 is preferably N,N-dimethyl, N,N-diethyl, N,N-dipropyl, N,N-diisopropyl, N,N-di-n-butyl, N,N-di-t.-butyl, N,N-dicyclohexyl or N,N-diphenyl.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • the present invention provides catalysts comprising at least one phosphonite ligand of the formula I wherein A combines with that part of the phosphonite group to which it is attached to form a 5- or 6-membered heterocycle which may optionally be singly or doubly fused with aryl and/or hetaryl, in which case the fused-on groups may bear one, two or three of the abovementioned substituents.
  • A is then for example a 2,2′-biphenylene, 2,2′-binaphthylene or 2,3-xylylene radical which may bear 1, 2 or 3 substituents selected from the group consisting of alkyl, alkoxy and halogen.
  • Alkyl here is preferably C 1 -C 4 -alkyl, especially t-butyl.
  • Alkoxy here is preferably C 1 -C 4 -alkoxy and especially methoxy.
  • Halogen is especially fluorine, chlorine or bromine.
  • R 1 is a radical of the formula II.1, II.2, II.3 or II.4:
  • R 2 and R 3 are independently hydrogen, alkyl, alkoxy, halogen, trifluoromethyl, nitro or cyano, and
  • R 4 is hydrogen, alkyl, preferably methyl, or aryl, preferably phenyl, which may optionally be substituted by alkyl, alkoxy, halogen, trifluoromethyl, nitro or cyano.
  • the phosphonite ligands of the formula I are selected from the group consisting of ligands of the formulae Ia to Ig
  • the catalysts of the present invention may include one or more of the phosphonite ligands of the formula I.
  • they may comprise at least one further ligand selected from the group consisting of halides, amines, carboxylates, acetylacetonate, arylsulfonates, alkylsulfonates, hydride, CO, olefins , dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics, heteroaromatics, ethers, PF 3 and phosphine, phosphinite, phosphonite and phosphite ligands, wherein the phosphine, phosphinite, phosphonite and phosphite ligands are monodentate, bidentate or polydentate.
  • further ligands may likewise be monodentate, bidentate or polydentate and coordinate to the metal atom of the catalyst complex.
  • suitable further phosphorus-containing ligands are customary phosphine, phosphininte and phosphite ligands.
  • m, A, D and R 1 are each as defined above.
  • a process for preparing these ligands is described in Phosphorus and Sulfur, 1987, vol. 31, pages 71 ff., for the construction of 6H-dibenz[c,e][ 1,2]oxaphosphorine ring systems.
  • Suitable alcohols of the formula HOR 1 OH are biphenyl-2,2′-diol and binaphthyl-2,2′-diol, for example. Further suitable diols are mentioned in U.S. Pat. No. 5,312,996, col. 19, incorporated herein by reference.
  • To prepare bidentate ligands of the formula I which bear one phosphonite and one phosphite group it is possible to react a compound of the formula IV with a compound of the formula HOR 1 OH to form a monocondensation product and then to react this monocondensation product with a compound of the formula V
  • the compounds of the formula IV may, if desired, be isolated and subjected to purification, for example by distillation.
  • the conversion of the compound of the formula III into a compound of the formula IV generally takes place at an elevated temperature within the range from about 40′ to about 200° C., and the reaction may also be carried out by gradually increasing the temperature.
  • a Lewis acid for example zinc chloride or aluminum chloride
  • a Lewis acid for example zinc chloride or aluminum chloride
  • the rest of the conversion of the compounds of the formula IV into the phosphonite ligands of the formula I used according to the present invention generally takes place in the presence of a base, for example an aliphatic amine, such as diethylamine, dipropylamine, dibutylamine, trimethylamine or tripropylamine and preferably triethylamine or pyridine.
  • the catalysts or catalyst precursors used in a particular case give rise under the conditions of a hydroformylation to catalytically active species of the general formula H x M y (CO) z L q , where M is a metal of the VIIIth transition group, L is a phosphonite ligand according to the present invention and q, x, y and z are each integers dependent on the valence and nature of the metal and the denticity of the ligand L.
  • z and q are independently at least 1, for example 1, 2 or 3.
  • the sum of z and q is preferably from 2 to 5.
  • the complexes may additionally comprise at least one of the above-described further ligands.
  • the metal M is preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium, especially cobalt, rhodium or ruthenium.
  • the hydroformylation catalysts are prepared in situ, in the reactor used for the hydroformylation reaction. If desired, however, the catalysts of the present invention may also be prepared separately and isolated in a conventional manner.
  • the in situ preparation of the catalysts of the present invention is effected by reacting at least one phosphonite ligand of the general formula I, a compound or a complex of a metal of the VIIIth transition group, optionally at least one further ligand, and optionally an activating agent in an inert solvent under the hydroformylation conditions.
  • rhodium(II) and rhodium(III) salts such as rhodium(III) chloride, rhodium(III) nitrate, rhodium(III) sulfate, potassium rhodium sulfate, rhodium(II) carboxylate, rhodium(III) carboxylate, rhodium(II) acetate, rhodium(III) acetate, rhodium(III) oxide, salts of rhodium(III) acid, triammonium hexachlororhodate(III), etc.
  • rhodium(II) and rhodium(III) salts such as rhodium(III) chloride, rhodium(III) nitrate, rhodium(III) sulfate, potassium rhodium sulfate, rhodium(II) carboxylate, rho
  • rhodium complexes such as rhodium biscarbonylacetylacetonate, acetylacetonatobisethylenerhodium(I), etc. Preference is given to using rhodium biscarbonylacetylacetonate or rhodium acetate.
  • Ruthenium salts or compounds are likewise suitable.
  • suitable ruthenium salts are ruthenium(III) chloride, ruthenium(IV) oxide, ruthenium(VI) oxide, ruthenium(VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K 2 RuO 4 or KRuO 4 or complexes of the general formula RuX 1 X 2 L 1 L 2 (L 3 ) n , where L 1 , L 2 , L 3 and n are each as defined above and X 1 and X 2 each have the meanings specified above for X, for example RuHCl(CO)(PPh 3 ) 3 .
  • metal carbonyls of ruthenium such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO is partly replaced by ligands of the formula PR 3 , such as Ru(CO) 3 (PPh 3 ) 2 , in the process of the present invention.
  • cobalt compounds examples include cobalt(II) chloride, cobalt(II) sulfate, cobalt(II) carbonate, cobalt(II) nitrate, their amine or hydrate complexes, cobalt carboxylates, such as cobalt acetate, cobalt ethylhexanoate, cobalt naphthanoate, and also the cobalt caprolactamate complex.
  • cobalt carboxylates such as cobalt acetate, cobalt ethylhexanoate, cobalt naphthanoate, and also the cobalt caprolactamate complex.
  • carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and hexacobalt hexadecacarbonyl.
  • activating agents are Bronsted acids, Lewis acids, for example BF 3 , AlCl 3 and ZnCl 2 , and Lewis bases.
  • the aldehydes which are formed from the respective olefins in the course of the hydroformylation, and their comparatively high boiling consecutive reaction products, for example the products of aldol condensation.
  • solvents there are preferably used the aldehydes which are formed from the respective olefins in the course of the hydroformylation, and their comparatively high boiling consecutive reaction products, for example the products of aldol condensation.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol
  • ketones such as acetone and methyl ethyl ketone, etc.
  • the molar ratio of phosphonite ligand of the general formula I to metal of the VIIIth transition group is generally within the range of about 1:1 to 1000:1.
  • the present invention further provides a process for hydroformylating compounds containing at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of at least one of the hydroformylation catalysts of the present invention.
  • Suitable substrates for the hydroformylation process of the present invention include in principle all compounds which contain one or more ethylenically unsaturated double bonds. These include for example olefins, such as ⁇ -olefins, internal straight-chain and internal branched olefins. Examples of suitable ⁇ -olefins are ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, etc.
  • olefins such as ⁇ -olefins, internal straight-chain and internal branched olefins.
  • suitable ⁇ -olefins are ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-
  • Suitable straight-chain internal olefins are preferably C 4 - to C 20 -olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene, etc.
  • Suitable branched internal olefins are preferably C 4 - to C 20 -olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched internal heptene mixtures, branched internal octene mixtures, branched internal nonene mixtures, branched internal decene mixtures, branched internal undecene mixtures, branched internal dodecene mixtures, etc.
  • olefins useful for hydroformylation are C 5 - to C 8 -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and derivatives thereof, for example their C 1 - to C 20 -alkyl derivatives having from 1 to 5 alkyl substituents.
  • olefins useful for hydroformylation are aromatic vinyl compounds, such as styrene, a-methylstyrene, 4-isobutylstyrene, etc.
  • olefins useful for hydroformylation are ⁇ , ⁇ -ethylenically unsaturated mono- and/or dicarboxylic acids, their esters, monoesters and amides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, methyl 3-pentenoate, methyl 4-pentenoate, methyl oleate, methyl acrylate, methyl methacrylate, unsaturated nitrites, such as 3-pentenenitrile, 4-pentenenitrile, acrylonitrile, vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., C 1 - to C 20 -alkenols, -alkenediols and -alkadienols, such as 2,7-octadien-1-ol.
  • mono- and/or dicarboxylic acids their esters, monoesters and
  • Suitable substrates further include di- or polyenes having isolated or conjugated double bonds. These include for example 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene and also butadiene homopolymers and copolymers.
  • the hydroformylation reaction may be carried out continuously, semicontinuously or batchwise.
  • Suitable reactors for the continuous reaction are known to the person skilled in the art and are described for example in Ullmanns Enzyklopädie der ischen Chemie, vol. 1, 3rd edition, 1951, pages 743 ff.
  • Suitable pressure-resistant reactors are likewise known to the person skilled in the art and are described for example in Ullmanns Enzyklopädie der ischen Chemie, vol. 1, 3rd edition, 1951, pages 769 ff.
  • the process of the present invention is carried out using an autoclave which, if desired, can be equipped with a stirrer and an internal lining.
  • composition of the carbon monoxide/hydrogen synthesis gas used in the process of the present invention may vary within wide limits.
  • the molar ratio of carbon monoxide to hydrogen is generally within the range from about 5:95 to 70:30, preferably within the range from about 40:60 to 60:40. Particular preference is given to using a molar ratio of carbon monoxide to hydrogen within the region of about 1:1.
  • the temperature of the hydroformylation reaction is generally within the range from about 20° to 180° C., preferably from about 50 to 150° C.
  • the reaction is generally carried out at the partial pressure of the reaction gas at the reaction temperature chosen.
  • the pressure will be within the range from about 1 to 700 bar, preferably within the range from 1 to 600 bar, especially within the range from 1 to 300 bar.
  • the reaction pressure may be varied as a function of the activity of the novel hydroformylation catalyst used.
  • the novel catalysts based on phosphonite ligands enable the reaction to take place within the region of lower pressures, for example within the range from 1 to 100 bar.
  • hydroformylation catalysts of the present invention may be separated from the hydroformylation reaction effluent by customary methods known to the person skilled in the art, and can generally be reused for the hydroformylation.
  • the catalysts of the present invention are advantageous in being very active, so that the corresponding aldehydes are generally obtained in good yields.
  • the catalysts of the present invention when used in the hydroformylation of ⁇ -olefins and of internal linear olefins they have very low selectivity with regard to the hydrogenation product of the olefin used.
  • catalysts of the present invention which comprise chiral phosphonite ligands of the formula I are useful for enantioselective hydroformylation.
  • Ligand Ic is prepared similarly to Example 1. The crude product obtained has a brown color and is slightly sticky. It is purified by vigorous stirring in n-hexane for 12 hours. The supernatant hexane solution is separated off to leave ligand Ic as a white powder.
  • the solid is repeatedly washed with small amounts of cold methyl tert-butyl ether. The remaining solid is taken up in degassed methylene chloride. The organic solution is repeatedly extracted with degassed water, dried over sodium sulfate and concentrated to dryness to leave a white solid.
  • Ligand Ib was prepared similarly to Example 3 and obtained as a white solid.
  • Ligand Ie was prepared similarly to Example 3 and obtained as a white solid.

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DE19810794A DE19810794A1 (de) 1998-03-12 1998-03-12 Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines Phosphonitliganden und Verfahren zur Hydroformylierung
PCT/EP1999/001597 WO1999046044A1 (de) 1998-03-12 1999-03-11 Katalysator, umfassend einen komplex eines metalls der viii. nebengruppe auf basis eines phosphonitliganden und verfahren zur hydroformylierung

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US20040073035A1 (en) * 2002-01-24 2004-04-15 Matthias Maase Method for the separation of acids from chemical reaction mixtures by means of ionic fluids
US20050101793A1 (en) * 2003-11-12 2005-05-12 Chung Shan Institute Of Science & Technology Method for preparing a biphenylphosphonate compound
US20050182277A1 (en) * 2002-05-10 2005-08-18 Oxen Olefinchemie Gmbh Method for the rhodium-catalyzed hydroformylation of olefins with reduction of rhodium losses
US20080154067A1 (en) * 2006-12-21 2008-06-26 Eastman Chemical Company Phosphonite-containing catalysts for hydroformylation processes
US20090171121A1 (en) * 2007-12-26 2009-07-02 Eastman Chemical Company Fluorophosphite containing catalysts for hydroformylation processes
US20090171122A1 (en) * 2007-12-26 2009-07-02 Eastman Chemical Company Phosphonite containing catalysts for hydroformylation processes
US7928267B1 (en) 2009-06-22 2011-04-19 Eastman Chemical Company Phosphite containing catalysts for hydroformylation processes
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WO2015094813A1 (en) 2013-12-19 2015-06-25 Dow Technology Investments Llc Hydroformylation process
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DE10046026A1 (de) * 2000-09-18 2002-03-28 Basf Ag Verfahren zur Hydroformylierung, Xanthen-verbrückte Liganden und Katalysator, umfassend einen Komplex dieser Liganden
US6660876B2 (en) 2001-11-26 2003-12-09 E. I. Du Pont De Nemours And Company Phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions
US6660877B2 (en) 2002-03-07 2003-12-09 E. I. Du Pont De Nemours And Company Phosphonite ligands and their use in hydrocyanation
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US7351339B2 (en) 2002-01-24 2008-04-01 Basf Aktiengesellschaft Method for the separation of acids from chemical reaction mixtures by means of ionic fluids
US20040073035A1 (en) * 2002-01-24 2004-04-15 Matthias Maase Method for the separation of acids from chemical reaction mixtures by means of ionic fluids
US20050182277A1 (en) * 2002-05-10 2005-08-18 Oxen Olefinchemie Gmbh Method for the rhodium-catalyzed hydroformylation of olefins with reduction of rhodium losses
US7232931B2 (en) 2002-05-10 2007-06-19 Oxeno Olefinchemie Gmbh Method for the rhodium-catalyzed hydroformylation of olefins with reduction of rhodium losses
US20050101793A1 (en) * 2003-11-12 2005-05-12 Chung Shan Institute Of Science & Technology Method for preparing a biphenylphosphonate compound
US7232921B2 (en) * 2003-11-12 2007-06-19 Chung Shan Institute Of Science & Technology Method for preparing a biphenylphosphonate compound
US20070213551A1 (en) * 2003-11-12 2007-09-13 Chung Shan Institute Of Science & Technology Method for preparing a Biphenylphosphonate compound
US7626051B2 (en) 2003-11-12 2009-12-01 Chung Shan Institute Of Science & Technology Method for preparing a biphenylphosphonate compound
US7586010B2 (en) 2006-12-21 2009-09-08 Eastman Chemical Company Phosphonite-containing catalysts for hydroformylation processes
US20080154067A1 (en) * 2006-12-21 2008-06-26 Eastman Chemical Company Phosphonite-containing catalysts for hydroformylation processes
US20090171121A1 (en) * 2007-12-26 2009-07-02 Eastman Chemical Company Fluorophosphite containing catalysts for hydroformylation processes
US20090171122A1 (en) * 2007-12-26 2009-07-02 Eastman Chemical Company Phosphonite containing catalysts for hydroformylation processes
US7872156B2 (en) 2007-12-26 2011-01-18 Eastman Chemical Company Fluorophosphite containing catalysts for hydroformylation processes
US7872157B2 (en) 2007-12-26 2011-01-18 Eastman Chemical Company Phosphonite containing catalysts for hydroformylation processes
US7928267B1 (en) 2009-06-22 2011-04-19 Eastman Chemical Company Phosphite containing catalysts for hydroformylation processes
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US8884072B2 (en) 2010-11-12 2014-11-11 Dow Technology Investments Llc Mitigation of fouling in hydroformylation processes by water addition
WO2012145241A1 (en) 2011-04-18 2012-10-26 Dow Technology Investments Llc Methods to store transition metal organophosphorous ligand based catalysts
US10478812B2 (en) 2011-04-18 2019-11-19 Dow Technology Investments Llc Methods to store transition metal organophosphorous ligand based catalysts
WO2013184350A1 (en) 2012-06-04 2013-12-12 Dow Technology Investments Llc Hydroformylation process
US9174907B2 (en) 2012-06-04 2015-11-03 Dow Technology Investments Llc Hydroformylation process
US9328047B2 (en) 2012-09-25 2016-05-03 Dow Technology Investments Llc Process for stabilizing a phosphite ligand against degradation
WO2014051975A1 (en) 2012-09-25 2014-04-03 Dow Technology Investments Llc Process for stabilizing a phosphite ligand against degradation
US9382180B2 (en) 2012-12-06 2016-07-05 Dow Technology Investments Llc Hydroformylation process
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WO2021126421A1 (en) 2019-12-19 2021-06-24 Dow Technology Investments Llc Processes for preparing isoprene and mono-olefins comprising at least six carbon atoms

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